Abstract
The kinetics of the Fe(CN)63−/Fe(CN)64− redox reaction on a polycrystalline gold electrode in KF solutions was studied by the potential step method. It was found that the apparent rate constant of this reaction changes approximately linearly with the KF concentration and that the apparent charge-transfer coefficient is a linear function of the electrode potential. The experimental results, which were analyzed considering the formation of ion pairs between the reactant and potassium cations and also considering the effect of the double layer can be interpreted on the basis of the quantum theory of the electron-transfer reaction through a bridge activated complex. The value of the reorganization energy of the classic subsystem λ=(0.47±0.06) eV calculated from our results is comparable with the λ value derived from the results of other authors.
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